CoSm(SeO3)2Cl, CuGd(SeO3)2Cl, MnSm(SeO3)2Cl, CuGd2(SeO3)4, and CuSm2(SeO3)4:: Transition metal containing selenites of samarium and gadolinum

The reaction of CoCl2, Sm2O3, and SeO2 in evacuated silica ampoules lead to blue single crystals of CoSm(SeO3)(2)Cl (tri-clinic, P (1) over bar, Z = 4, a = 712.3(1), b = 889.5(2), c = 1216.2(2) pm, alpha = 72.25(1)degrees, beta = 71.27(1)degrees, gamma = 72.08(1)degrees, R-all = 0.0586). If MnCl2 is used in the reaction light pink single crystals of MnSm(SeO3)(2)Cl (triclinic, P (1) over bar, Z = 2, a = 700.8(2), b = 724.1(2), c = 803.4(2) pm, alpha = 86.90(3)degrees, beta = 71.57(3)degrees, gamma = 64.33(3)degrees, R-all = 0.0875) are obtained. Green single crystals of CuGd2(SeO3)(2)Cl (triclinic, P (1) over bar, Z = 4, a = 704.3(4), b = 909.6(4), c = 1201.0(7) pm, alpha = 70.84(4)degrees, beta = 73.01(4)degrees, gamma = 70.69(4)degrees, R-all = 0.0450) form analogously in the reaction of CuCl2 and Gd2O3 with SeO2. CoSm(SeO3)ZCl contains [CoO4Cl2] octahedra, which are connected via one edge and one vertex to infinite chains. The Mn2+ ions in MnSm(SeO3)(2)Cl are also octahedrally coordinated by four oxygen and two chlorine ligands. The linkage of the polyhedra to chains occurs exclusively via edges. Both, the cobalt and the manganese compound show the Sm3+ ions in eight and ninefold coordination of oxygen atoms and chloride ions. In CuGd(SeO3)(2)Cl the Cu2+ ions are coordinated by three oxygen atoms and one Cl- ion in a distorted square planar manner. One further Cl- and one further oxygen ligand complete the [CuO3Cl] units yielding significantly elongated octahedra. The latter are again connected to chains via two common edges. For the Gd3+ ions coordination numbers of "8 + 1" and nine were found. Single crystals of the deep blue selenites CuM2(SeO3)(4) (M = Sm/Gd, monoclinic, P2(1)/c, a = 1050.4(3)/1051.0(2), b = 696.6(2)/693.5(1), c = 822.5(2)/818.5(2) pm, beta = 110.48(2)degrees/110.53(2)degrees, R-all = 0.0341/0.0531) can be obtained from reactions of the oxides Sm2O3 and Gd2O3, respectively, with CuO and SeO2. The crystal structure contains square planar [CuO4] groups and irregular [MO9] polyhedra.